Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
  • C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
  • C08G63/6956—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

• the subject of the present invention is copolyesters with oxysulfonyl groups and with siloxane units which can be used in particular for the coating of shaped objects based on linear polyesters, such as films and fibers.
• Linear copolyesters with oxysulfonyl groups with siloxane units are known which can be used to obtain fibers with improved dye affinity with respect to basic dyes.
• Such copolyesters have been described in the Japanese patent application published under the number 61/124 625. They are characterized by the presence in their chains of 0.5 to 2 mole%, based on the total of unsulfonated dicarboxylic acid units and non-silicone, of 5-isophthalate units and by a content by weight of polysiloxane units of between 1 and 20%.
• the polysiloxane units are introduced into the copolyester chain from polysiloxanediols or from compounds (ethers, esters) releasing polysiloxanediols during the process of obtaining the copolyesters.
• polyester films it is sought to modify the surface properties of the film without modifying the structure of the polyester which constitutes it so as to retain its mechanical properties.
• polyester films intended for the manufacture of magnetic tapes good sliding properties without modification of the chemical structure of the polyester.
• One of the means which makes it possible to achieve such an objective resides in the deposition on the surface of the films of a coating capable of giving it new surface properties. This coating must meet various requirements, in particular as regards its ease of implementation, its thermal stability under the conditions for obtaining the films, its adhesion to polyester films.
• Aqueous coating compositions are particularly sought after.
• the copolyesters with oxysulfonyl groups and with polysiloxane units described in the aforementioned Japanese patent application do not meet the requirements noted above, so that the industry is looking for polymers capable of being deposited on the surface of polyester films in the form of aqueous compositions, exhibiting good adhesion to polyester support films, thermally stable under filming conditions and giving said polyester support films good sliding properties.
• the present invention specifically relates to sulfonated copolyesters containing siloxane units which meet these various requirements.
• oxysulfonyl group denotes, under the present invention, groups of general formula: - (SO3) n1 M (II) in which : . n1 is 1 or 2 .
• M represents a hydrogen atom, an alkali or alkaline earth metal, an ammonium or quaternary ammonium cation.
• copolyesters with oxysulfonyl groups and with siloxane units according to the present invention will hereinafter be referred to as silicone sulfonated copolyesters for reasons of convenience. They are obtained according to the usual processes for the preparation of linear polyesters from at least one dicarboxylic acid or its derivatives (esters of lower aliphatic alcohols, halides), from at least one diol, from at least one dicarboxylic acid and / or a diol carrying one or more oxysulfonyl groups and at least one difunctional compound (diacid, diol, acid-alcohol) containing siloxane units.
• the term “lower alcohol” and “aliphatic or lower alkoxy radical” will be used hereinafter to denote alcohols and radicals containing from 1 to 4 carbon atoms.
• the dicarboxylic acids which can be used to obtain the silicone sulfonated copolyesters according to the present invention can be saturated aliphatic diacids containing from 4 to 15 carbon atoms such as adipic, succinic, sebacic, azelaic, glutaric or suberic acids or diacids aromatics such as the acids usually used for the preparation of linear polyesters; as such, there may be mentioned, as nonlimiting examples, terephthalic, isophthalic, phthalic, naphthalenedicarboxylic-2,5, naphthalenedicarboxylic-2,7, diphenyldicarboxylic-4,4 ′, bis-hydroxycarbonyl-4,4 ′ diphenylsulfone .
• aromatic diacids use is preferably made of aromatic diacids alone or in admixture with one another or associated with a minor amount of one or more alkanedicarboxylic acids, the aromatic dicarboxylic acids preferably representing at least 80 mol% of the total of the free diacids of oxysulfonyl groups.
• Terephthalic and / or isophthalic acids are particularly suitable.
• the diols which can be used for the preparation of the copolyesters according to the invention are those usually used for obtaining linear polyesters. Mention may be made, by way of examples, of alkanediols such as ethylene glycol, propanediol-1,3, butanediol-1,4, butanediol-1,3, dimétyl-2,2 propanediol -1,3 , pentanedlol-1,5, polyoxylalkylenediols such as di-, tri-, tetra-, decaoxyethylene glycols, cycloalkane diols, diols with cycloalkylene groups such as cyclohexanedimethanol-4,4 ′.
• alkanediols such as ethylene glycol, propanediol-1,3, butanediol-1,4, butanediol-1,3, dimétyl-2,2 propanediol -1,
• diols can be used alone or as a mixture.
• the lower alkanediols are used alone or as a mixture with one another and optionally combined with more carbon-condensed diols such as neopentylglycol, cyclohexanedimethanol and polyoxyethylene glycols.
• the presence in the chain of the copolyesters according to the invention of units derived from polyoxyalkylene glycols, of formula Ho [(CH 2) x 0] H n2 in which x is an integer from 2 to 4 and n2 an integer from 2 to 10 and in particular those of formula HO (CH2CH2 - O] n2H- proves to be advantageous for lowering their viscoelasticity.
• the first preferably represent at least 50% by moles of the total of the mixture of said diols.
• the copolyesters according to the invention comprise at least 80% by moles of terephthalate, isophthalate or naphthalenedicarboxylate units.
• ethylene glycol reported in 100 moles of units derived from diols.
• the oxysulfonyl groups of formula (II) are introduced into the polyester via a difunctional compound with an oxysulfonyl group, capable of reacting with the diacids and / or the diols during the polycondensation.
• dicarboxylic acids or diols containing one or more oxysulfonyl groups can be used, preferably in the form of alkaline salts.
• - M and n1 have the meaning already given;
• - Q is a versatile aromatic radical;
• - X and Y are hydroxycarbonyl radicals or derivatives: esters of lower aliphatic alcohols or acid halides (chloride, bromide);
• - p is an integer equal to 1 or 2.
• Q more specifically represents a phenyl radical or a combination of 2 or more of 2 ortho or pericondensed phenyl radicals or of two or more phenyl groups linked together by inert groups such as alkylidene (propylidene) radicals or ether, ketone, sulfone groups.
• dicarboxylic acids with oxysulfonyl groups mention may be made of hydroxysulfonylterephthalic acids hydroxysulfonylisophthalic (in particular, 5-isophalic acid); hydroxysulfonylorthophthalic; hydroxysulfonyl-4, naphthalene-dicarboxylic-2,7; hydroxysulfonyldiphenyl-dicarboxylic-4,4 ′; hydroxysulfonyl di-hydroxycarbonyl-4,4 ′ diphenylsulfones; hydroxysulfonyldihydroxycarbonyl-4,4 ′ diphenylmethanes; isophthalic acid (hydroxysulfonylphenoxy) - 5, isophthalic acid (hydroxysulfonylpropoxy) - 5.
• hydroxysulfonylterephthalic acids hydroxysulfonylisophthalic (in particular, 5-isophalic acid);
• the dicarboxylic acids with oxysulfonyl groups can be used in their acid form or, preferably in the form of their derivatives (halides or lower alkyl esters) capable of generating polyesters.
• methyl diesters are used.
• the sulfonic group (s) of the diacid or of its derivatives is (are) preferably in the form of alkaline salts.
• the siloxane units are introduced into the chain of copolyesters according to the invention by a difunctional compound with siloxane units capable of reacting with the diols and / or dicarboxylic acids, or their derivatives, used to obtain the copolyesters. More specifically, difunctional compounds of general formula are used: In which : - R1, R2, R3, R4, A and n have the meaning given above; - Z ′ and Z ⁇ , identical or different, represent a hydroxyl group, a hydroxycarbonyl group, a lower alkoxycarbonyl group, a halocarbonyl group (chloro or bromo).
• R1, R2, R3, R4 represent linear or branched alkyl radicals having from 1 to 16 carbon atoms such as methyl radicals; ethyl; n-propyl; isopropyl; n-butyl; isobutyl; n-pentyl; 2-ethylhexyl: n-decyl: cycloalkyl radicals containing from 5 to 15 carbon atoms such as the cyclopentyl, cyclohexyl radicals; arylalkyl radicals in which the alkyl part contains from 1 to 15 carbon atoms, such as 2-phenylethyl. .
• A represents alkylene radicals having from 1 to 15 carbon atoms such as methylene radicals; ethylene; ethylidene; propylene-1,3; 1,4-butylene; ⁇ -1,3-methylpropylene; 1,5-pentylene hexamethylene, decamethylene; radicals consisting of a chain of one or more arylene radicals (o, m or p -phenylene optionally substituted by one or more lower alkyl radicals) and one or more alkylene radicals having from 1 to 15 carbon atoms such as those mentioned above; as such, mention may be made, by way of example, of groups of formulas: - Arylene radicals consisting of one or more ortho or pericondensed phenyl radicals such as the phenylene, diphenylene, naphthylene radicals, optionally substituted by one or more lower alkyl radicals.
• n represents an integer or fractional number between 8 and 100 and preferably between 10 and 80.
• the difunctional compounds of formulas (IV) are known products which can be prepared by the usual routes for the synthesis of organosilicon compounds. It is possible, for example, to react a compound with siloxane units and with terminal hydrogenosilyl groups with a functional organic compound containing ethylenic unsaturation, in the presence of platinum, or alternatively to bring an organo dialkylmonochlorosilane with functional group into contact with a polysiloxanediol or its ether derivatives. 'lower alkyl.
• the sulfonated copolyesters containing siloxane units according to the invention can be obtained by the usual methods for obtaining linear polyesters known to those skilled in the art.
• one or more dicarboxylic acids or derivatives esters, lower alkyl, halides
• at least one diol, at least one difunctional compound with oxysulfonyl group (s) and at least one compound of formula (IV) in the presence of the usual catalysts for esterification or transesterifications
• polycondensation is carried out in the presence of the usual catalysts.
• the temperature and pressure conditions are those generally implemented for each of the two stages, thus the first stage can be carried out at a temperature between approximately 150 and 250 ° C. and the second between 210 and 280 ° C, the sub- reaction products being continuously removed by distillation under reduced pressure; preferably the first and second stages are carried out at temperatures between 180 and 200 ° C respectively and between 220 and 250 ° C.
• the respective amounts of the various monomers constituting the final copolyester used depend on the properties desired for the latter. Generally, the amount of difunctional compound with oxysulfonyl group, expressed in moles per 100 moles of non-sulfonated and non-silicone difunctional compound of the same nature must be sufficient to give the final copolyester a hydrophilic nature such that it can be easily dispersed in water, giving stable aqueous suspensions.
• a quantity of monomer containing an oxysulfonyl group representing more than 2% by mole of the difunctional non-sulfonated and non-silicone compounds of the same nature makes it possible to achieve this objective.
• the amount of monomer containing an oxysulfonyl group is between 5 and 25 mol% and, more preferably still between 7 and 20%.
• the amount of difunctional compound containing siloxane units depends on the silicon content desired for the final polymer, expressed as a percentage by weight of silicon relative to the silicone sulfonated copolyester.
• the silicon content is determined as a function of the properties sought for the final polymer and in particular of its physicochemical surface properties. In general, it is sought to introduce from 0.05 to 5% by weight of silicon in the copolyester and, preferably, from 0.1 to 2.5% by weight.
• the quantity of difunctional monomers containing siloxane units used to achieve this objective must also take into account the degree of conversion of said monomer and / or side reactions which are variable according to the reaction conditions. This quantity can be easily determined in each particular case by means of simple tests. In general, it is advantageous to use an excess of difunctional compound with siloxane units relative to the stoichiometric quantity theoretically necessary to achieve the desired level of silicon.
• the total quantity of diols alkylene glycol and, where appropriate, diol containing oxysulfonyl group (s) and / or diol containing siloxane units, is at least close to the stoichiometric quantity, that is to say close to 1 mole of diols per mole of diacid (s); however, it is preferred to use an excess of diol (s) relative to the diacid (s).
• the amount of alkylenediol (s) used is between 1.5 and 3 moles per mole of diacid (s).
• copolyesters of the present invention those which have in their chain a plurality of polyoxylkylene units, and more particularly of polyoxyethyne units of formula: - [O - CH2 - CH2] n2 - in which n2 is an integer between 2 and 10, are particularly advantageous.
• the presence of such patterns makes it possible to modify the viscoelastic properties of the copolyester and consequently to favorably influence the adhesion properties of coatings based on the copolyesters according to the invention to conventional linear polyesters.
• the silicone sulfonated copolyesters which are the subject of the present application can therefore preferably contain an effective amount of a polyoxyalkylene diol and in particular of a polyoxyethylene glycol to modify the viscoelastic properties thereof.
• an amount of polyoxyalkylene diol representing from 1% by weight to 40% by weight of copolyester and, preferably from 5% by weight to 25% by weight, is suitable.
• polyoxyalkylene diol units into the chain of silicone sulfonated copolyesters can be obtained by using an adequate quantity of a preformed polyoxyalkylene diol or by its in situ formation from an alkylene glycol by virtue of the choice of the conditions of reaction and polycondensation which are well known to those skilled in the art (for example: temperature, excess glycol, acidity of the medium).
• the silicone sulfonated copolyesters which constitute the subject of the present invention can be advantageously used for coating polyester films and in particular films of polyethylene terephatalate.
• copolyester (A) The properties of the copolyester (A) are shown in Tables I to IV below.
• the following quantities of reagents were loaded: DMT: 1280 g IMD: 329 g DMIS Na: 329 g EG: 1334 ml Catalyst: 0.35 g Oligomer (B): 61 g (0.036 mole)
• Example No. 2 is reproduced here by loading the following quantities of reagents: DMT: 1280 g IMD: 329 g DMIS Na: 329 g EG: 1130 ml Catalyst: 0.35g Compound (B): 61 g (0.036 mole)
• Example n ° 2 is reproduced here by introducing twice as little of compound (B): DMT: 1,301 g (6.7 moles) IMD: 354 g (1.823 mole) DMIS Ma: 334 g (1.127 mole) EG: 1,353 ml (24 moles) Catalyst: 0.35 g Compound (B): 30.50 g (0.0179 mole)
• Example No. 1 The procedure is as in Example No. 1 using a polysiloxane compound (C) of formula similar to that of (A) but of which n is equal to 13.72 and of diethylene glycol (DEG) in order to modify its viscoelasticity.
• C polysiloxane compound of formula similar to that of (A) but of which n is equal to 13.72 and of diethylene glycol (DEG) in order to modify its viscoelasticity.
• Example No. 1 is reproduced here in which (A) has been replaced by (C) by increasing the amount of polysiloxane compound (C).
• copolyesters have a Tg at - 100 ° C. which corresponds to the polysiloxane phase.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Silicon Polymers (AREA)
• Polyesters Or Polycarbonates (AREA)

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Citations (4)

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• 1989
  • 1989-11-21 FR FR8915531A patent/FR2654733B1/fr not_active Expired - Fee Related
• 1990
  • 1990-11-20 ES ES90420503T patent/ES2085343T3/es not_active Expired - Lifetime
  • 1990-11-20 AT AT90420503T patent/ATE133433T1/de not_active IP Right Cessation
  • 1990-11-20 DK DK90420503.6T patent/DK0430828T3/da active
  • 1990-11-20 DE DE69025044T patent/DE69025044T2/de not_active Expired - Fee Related
  • 1990-11-20 EP EP90420503A patent/EP0430828B1/de not_active Expired - Lifetime
• 1996
  • 1996-03-20 GR GR960400770T patent/GR3019370T3/el unknown

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